Organic light-emitting diode comprising amine-based compounds and pyrene-based compounds

ABSTRACT

An organic light-emitting diode includes a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode. The organic layer includes an emission layer. The organic layer also includes at least one amine-based compound and at least one pyrene-based compound. The organic layer may include a first emission layer and a second emission layer, and the amine-based compound may be in the first emission layer and the pyrene-based compound may be in the second emission layer.

CROSS-REFERENCE TO RELATED PATENT APPLICATION

This application claims priority to and the benefit of Korean PatentApplication No. 10-2013-0003513, filed on Jan. 11, 2013 in the KoreanIntellectual Property Office, the entire content of which isincorporated herein by reference.

BACKGROUND

1. Technical Field

The present invention relates to organic light-emitting diodescomprising amine-based compounds and pyrene-based compounds.

2. Description of the Related Art

Organic light-emitting devices (OLEDs) are self-emitting devices thathave advantages such as wide viewing angles, good contrast, quickresponse speeds, high brightness, and good driving voltagecharacteristics. Also, OLEDs can provide multicolored images.

A typical OLED has a structure including a substrate, and an anode, ahole transport layer (HTL), an emission layer (EML), an electrontransport layer (ETL), and a cathode sequentially stacked on thesubstrate. In this regard, the HTL, the EML, and the ETL are organicthin films formed of organic compounds.

An operating principle of an OLED having the above-described structureis as follows:

When a voltage is applied between the anode and the cathode, holesinjected from the anode move to the EML via the HTL, and electronsinjected from the cathode move to the EML via the ETL. The holes andelectrons recombine in the EML to generate excitons. When the excitonsdrop from an excited state to a ground state, light is emitted.

SUMMARY OF THE INVENTION

Embodiments of the present invention are directed to a high definitionorganic light-emitting diode

According to another aspect of the present invention, an organiclight-emitting device includes: a first electrode; a second electrode,and an organic layer between the first electrode and the secondelectrode and including an emission layer. The organic layer includes atleast one amine-based compound represented by Formula 1 below and atleast one pyrene-based compound represented by Formula 2 below.

In Formula 1 and 2, X₁ to X₄ are each independently a substituted orunsubstituted C₃-C₁₀ cycloalkylene group, a substituted or unsubstitutedC₂-C₁₀ heterocycloalkylene group, a substituted or unsubstituted C₃-C₁₀cycloalkenylene group, a substituted or unsubstituted C₂-C₁₀cycloalkenylene group, a substituted or unsubstituted C₆-C₆₀ arylenegroup, or a substituted or unsubstituted C₂-C₆₀ heteroarylene group.

n1 to n4 are each independently an integer of 0 to 5. If n1 is aninteger of 2 or more, then the 2 or more X₁ groups are the same ordifferent, if n2 is an integer of 2 or more, then the 2 or more X₂groups are the same or different, if n3 is an integer of 2 or more, thenthe 2 or more X₃ groups are the same or different, and if n4 is aninteger of 2 or more, then the 2 or more X₄ groups are the same ordifferent.

Y₁ to Y₄ are each independently a substituted or unsubstituted C₃-C₁₀cycloalkylene group, a substituted or unsubstituted C₂-C₁₀heterocycloalkyl group, a substituted or unsubstituted C₃-C₁₀cycloalkenyl group, a substituted or unsubstituted C₂-C₁₀ cycloalkenylgroup, a substituted or unsubstituted C₆-C₃₀ aryl group, or asubstituted or unsubstituted C₂-C₃₀ heteroarylene group.

Z₁ and Z₂ are electron transporting groups and are each independently asubstituted or unsubstituted C₂-C₁₀ heterocycloalkyl group, asubstituted or unsubstituted C₂-C₁₀ heterocycloalkenyl group, or asubstituted or unsubstituted C₂-C₆₀ heteroaryl group.

R₁ to R₄ are each independently a hydrogen atom, a deuterium atom, ahalogen atom, a hydroxyl group, a cyano group, a nitro group, an aminogroup, an amidino group, a hydrazine, a hydrazone, a carboxylic acidgroup or a salt thereof, a sulfonic acid group or a salt thereof, aphosphoric acid group or a salt thereof, a substituted or unsubstitutedC₁-C₆₀ alkyl group, a substituted or unsubstituted C₂-C₆₀ alkenyl group,a substituted or unsubstituted C₂-C₆₀ alkynyl group, a substituted orunsubstituted C₁-C₆₀ alkoxy group, a substituted or unsubstituted C₃-C₁₀cycloalkyl group, a substituted or unsubstituted C₂-C₁₀ heterocycloalkylgroup, a substituted or unsubstituted C₃-C₁₀ cycloalkenyl group, asubstituted or unsubstituted C₂-C₁₀ heterocycloalkenyl group, asubstituted or unsubstituted C₆-C₆₀ aryloxy group, a substituted orunsubstituted C₆-C₆₀ arylthio group, or a substituted or unsubstitutedC₂-C₆₀ heteroaryl group.

a1 to a4 are each independently an integer of 0 to 4. If a1 is aninteger of 2 or more, then the 2 or more R₁ groups are the same ordifferent, if a2 is an integer of 2 or more, then the 2 or more R₂groups are the same or different, if a3 is an integer of 2 or more, thenthe 2 or more R₃ groups are the same or different, and if a4 is aninteger of 2 or more, then the 2 or more R₄ groups are the same ordifferent.

b1 and b2 are each independently an integer of 0 or 1.

The organic light-emitting diode including the amine-based compound andthe pyrene-based compound may have high efficiency and a long lifespan.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other features and advantages of the present inventionwill become more apparent by reference to the following detaileddescription, when considered in conjunction with the attached drawingsin which:

FIG. 1 is a schematic view of a structure of an organic light-emittingdiode according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

In the present specification, the expression “organic layer includes atleast one amine-based compound represented by Formula 1 and at least onepyrene-based compound represented by Formula 2” may be construed as “theorganic layer includes one amine-based compound of Formula 1 or twodifferent amine-based compounds of Formula 1, one pyrene-based compoundof Formula 2 or two different pyrene-based compounds of Formula 2.”

In the present specification, the term “organic layer” refers to asingle layer and/or a plurality of layers between a first electrode anda second electrode.

An organic light-emitting diode includes a first electrode; a secondelectrode, and an organic layer between the first electrode and thesecond electrode. The organic layer includes an emission layer includingat least one amine-based compound represented by Formula 1 below and atleast one pyrene-based compound represented by Formula 2 below.

In Formulas 1 and 2, X₁ to X₄ are each independently a substituted orunsubstituted C₃-C₁₀ cycloalkylene group, a substituted or unsubstitutedC₂-C₁₀ heterocycloalkylene group, a substituted or unsubstituted C₃-C₁₀cycloalkenylene group, a substituted or unsubstituted C₂-C₁₀cycloalkenylene group, a substituted or unsubstituted C₆-C₆₀ arylenegroup, or a substituted or unsubstituted C₂-C₆₀ heteroarylene group.

n1 to n4 are each independently an integer of 0 to 5. If n1 is aninteger of 2 or more, the 2 or more X₁ groups are the same or different,if n2 is an integer of 2 or more, the 2 or more X₂ groups are the sameor different, if n3 is an integer of 2 or more, the 2 or more X₃ groupsare the same or different, and if n4 is an integer of 2 or more, the 2or more X₄ groups are the same or different.

Y₁ to Y₄ are each independently a substituted or unsubstituted C₃-C₁₀cycloalkyl group, a substituted or unsubstituted C₂-C₁₀ heterocycloalkylgroup, a substituted or unsubstituted C₃-C₁₀ cycloalkenyl group, asubstituted or unsubstituted C₂-C₁₀ heterocycloalkenyl group, asubstituted or unsubstituted C₆-C₃₀ aryl group, or a substituted orunsubstituted C₂-C₃₀ heteroaryl group.

Z₁ and Z₂ are electron transporting groups and are each independently asubstituted or unsubstituted C₂-C₁₀ heterocycloalkyl group, asubstituted or unsubstituted C₂-C₁₀ heterocycloalkenyl group, or asubstituted or unsubstituted C₂-C₆₀ heteroaryl group.

R₁ to R₄ are each independently selected from a hydrogen atom, adeuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitrogroup, an amino group, an amidino group, a hydrazine, a hydrazone, acarboxylic acid group or a salt thereof, a sulfonic acid group or a saltthereof, a phosphoric acid group or a salt thereof, a substituted orunsubstituted C₁-C₆₀ alkyl group, a substituted or unsubstituted C₂-C₆₀alkenyl group, a substituted or unsubstituted C₂-C₆₀ alkynyl group, asubstituted or unsubstituted C₁-C₆₀ alkoxy group, a substituted orunsubstituted C₃-C₁₀ cycloalkyl group, a substituted or unsubstitutedC₂-C₁₀ heterocycloalkyl group, a substituted or unsubstituted C₃-C₁₀cycloalkenyl group, a substituted or unsubstituted C₂-C₁₀heterocycloalkenyl group, a C₆-C₆₀ aryl group, a substituted orunsubstituted C₆-C₆₀ aryloxy group, a substituted or unsubstitutedC₆-C₆₀ arylthio group, or a substituted or unsubstituted C₂-C₆₀heteroaryl group.

a1 to a4 are each independently an integer of 0 to 4. If a1 is aninteger of 2 or more, the 2 or more R₁ groups are the same or different,if a2 is an integer of 2 or more, the 2 or more R₂ groups are the sameor different, if a3 is an integer of 2 or more, the 2 or more R₃ groupsare the same or different, and if a4 is an integer of 2 or more, the 2or more R₄ groups are the same or different.

b1 and b2 are each independently an integer of 0 or 1.

According to an embodiment of the present invention, in Formulas 1 and2, X₁ to X₄ may each independently be a substituted or unsubstitutedC₃-C₁₀ cycloalkylene group, a substituted or unsubstituted C₂-C₁₀heterocycloalkylene group, a substituted or unsubstituted C₃-C₁₀cycloalkenylene group, a substituted or unsubstituted C₂-C₁₀heterocycloalkenylene group, a substituted or unsubstituted C₆-C₆₀arylene group, or a substituted or unsubstituted C₂-C₆₀ heteroarylenegroup, but X₁ to X₄ are not limited thereto.

For example, in Formulas 1 and 2, X₁ to X₄ may each independently be asubstituted or unsubstituted phenylene group, a substituted orunsubstituted pentalenylene group, a substituted or unsubstitutedindenylene group, a substituted or unsubstituted naphthylene group, asubstituted or unsubstituted azulenylene group, a substituted orunsubstituted heptalenylene group, a substituted or unsubstitutedindacenylene group, a substituted or unsubstituted acenaphthylene group,a substituted or unsubstituted fluorenylene group, a substituted orunsubstituted phenalenylene group, a substituted or unsubstitutedphenanthrenylene group, a substituted or unsubstituted anthrylene group,a substituted or unsubstituted fluoranthenylene group, a substituted orunsubstituted triphenylenylene group, a substituted or unsubstitutedpyrenylene group, a substituted or unsubstituted chrysenylene group, asubstituted or unsubstituted naphthacenylene group, a substituted orunsubstituted picenylene group, a substituted or unsubstitutedperylenylene group, a substituted or unsubstituted pentaphenylene group,a substituted or unsubstituted hexacenylene group, a substituted orunsubstituted pyrrolylene group, a substituted or unsubstitutedimidazolylene group, a substituted or unsubstituted pyrazolylene group,a substituted or unsubstituted pyridinylene group, a substituted orunsubstituted pyrazinylene group, a substituted or unsubstitutedpyrimidinylene group, a substituted or unsubstituted pyridazinylenegroup, a substituted or unsubstituted isoindolylene group, a substitutedor unsubstituted indolylene group, a substituted or unsubstitutedindazolylene group, a substituted or unsubstituted indazolylene group, asubstituted or unsubstituted purinylene group, a substituted orunsubstituted quinolinylene group, a substituted or unsubstitutedbenzoquinolinylene group, a substituted or unsubstituted phthalazinylenegroup, a substituted or unsubstituted naphthyridinylene group, asubstituted or unsubstituted quinoxalinylene group, a substituted orunsubstituted quinazolinylene group, a substituted or unsubstitutedcinnolinylene group, a substituted or unsubstituted carbazolylene group,a substituted or unsubstituted phenanthridinylene group, a substitutedor unsubstituted acridinylene group, a substituted or unsubstitutedphenanthrolinylene group, a substituted or unsubstituted phenazinylenegroup, a substituted or unsubstituted benzooxazolylene group, asubstituted or unsubstituted benzoimidazolylene group, a substituted orunsubstituted furanylene group, a substituted or unsubstitutedbenzofuranylene group, a substituted or unsubstituted thiophenylenegroup, a substituted or unsubstituted benzothiophenylene group, asubstituted or unsubstituted thiazolylene group, a substituted orunsubstituted isothiazolylene group, a substituted or unsubstitutedbenzothiazolylene group, a substituted or unsubstituted isoxazolylenegroup, a substituted or unsubstituted oxazolylene group, a substitutedor unsubstituted triazolylene group, a substituted or unsubstitutedtetrazolylene group, a substituted or unsubstituted oxadiazolylenegroup, a substituted or unsubstituted triazinylene group, a substitutedor unsubstituted benzooxazolylene group, a substituted or unsubstituteddibenzopuranylene group, a substituted or unsubstituteddibenzothiophenylene group, or a substituted or unsubstitutedbenzocarbazolylene group, but X₁ to X₄ are not limited thereto.

For example, in Formulas 1 and 2, X₁ to X₄ may each independently be i)a phenylene group, a naphthylene group, an anthracenylene group, or afluorenylene group; or ii) a phenylene group, a naphthylene group, ananthracenylene group, a fluorenylene group, or a C₁-C₁₀ alkyl group; aC₁-C₁₀ alkyl group substituted with at least one of a deuterium atom, ahalogen atom, a hydroxyl group, a cyano group, a nitro group, an aminogroup, an amidino group, a hydrazine, a hydrazone, a carboxylic acidgroup or a salt thereof, a sulfonic acid group or a salt thereof, aphosphoric acid group or a salt thereof; a C₆-C₁₆ aryl group or a C₂-C₁₆heteroaryl group; a C₆-C₁₆ aryl group or a C₂-C₁₆ heteroaryl groupsubstituted with at least one of a deuterium atom, a halogen atom, ahydroxyl group, a cyano group, a nitro group, an amino group, an amidinogroup, a hydrazine, a hydrazone, a carboxylic acid group or a saltthereof, a sulfonic acid or a salt thereof, a phosphoric acid or a saltthereof, a C₁-C₆₀ alkyl group, a C₂-C₆₀ alkenyl group, a C₂-C₆₀ alkynylgroup, a C₁-C₆₀ alkoxy group, a C₆-C₁₆ aryl group, or C₂-C₁₆ heteroarylgroup, but X₁ to X₄ are not limited thereto.

For example, in Formulas 1 and 2, X₁ to X₄ may each independently beselected from i) a phenylene group or a naphthylene group; ii) aphenylene group or a naphthylene group substituted with at least one ofa deuterium atom, —F, a cyano group, a nitro group, a methyl group, anethyl group, an n-propyl group, an iso-propyl group, an n-butyl group,an iso-butyl group, or a tert-butyl group; iii) a phenylene group or anaphthylene group substituted with at least one of a deuterium atom, —F,a cyano group, a nitro group, a methyl group, an ethyl group, ann-propyl group, an iso-propyl group, an n-butyl group, an iso-butylgroup, or a tert-butyl group; an n-butyl group, an iso-butyl group, or atert-butyl group; iv) a phenylene group or a naphthylene groupsubstituted with at least one of a phenyl group, a naphthyl group, ananthracenyl group, or a fluorenyl group; or v) a phenylene group or anaphthylene group substituted with at least one of a deuterium atom, —F,a cyano group, a nitro group, a methyl group, an ethyl group, ann-propyl group, an iso-propyl group, an n-butyl group, an iso-butylgroup, a tert-butyl group, a pyrrolyl group, an imidazolyl group, atriazolyl group, an isoindolyl group, an indolyl group, an indazolylgroup, a purinyl group, a benzoimidazolyl group, an oxazolyl group, anisoxazolyl group, an oxadiazolyl group, or a benzoxazolyl group, but X₁to X₄ are not limited thereto.

For example, X₁ to X₄ in Formulas 1 and 2 may each independently be atleast one group represented by one of Formulas 4a to 4d below, but arenot limited thereto:

In Formulas 4a to 4d, R₄₁ to R₄₄ may each independently be a deuteriumatom, —F, a cyano group, a methyl group, an ethyl group, an n-propylgroup, an iso-propyl group, an n-butyl group, an iso-butyl group, or atert-butyl group.

d1 is an integer of 0 to 4. If d1 is an integer of 2 or more, the 2 ormore R₄₁ groups are the same or different.

d2 to d4 are each independently an integer of 0 to 6. If d2 is aninteger of 2 or more, the 2 or more R₄₂ group are the same or different,if d3 is a integer of 2 or more, the 2 or more R₄₃ groups are the sameor different, and if d4 is a integer of 2 or more, the 2 or more R₄₄groups are the same or different.

* is a bonding site to a pyrene ring, and *′ is a bonding site to N, Z₁or Z₂.

According to an embodiment of the present invention, in Formulas 1 and2, n1, n2, n3 and n4 represent the numbers of X₁ groups, X₂ groups, X₃groups and X₄ groups, respectively. n1 to n4 are each independently aninteger of 0 to 5. If n1 is an integer of 2 or more, the 2 or more X₁groups may be the same or different, if n2 is an integer of 2 or more,the 2 or more X₂ groups may be the same or different, if n3 is aninteger of 2 or more, the 2 or more X₃ groups may be the same ordifferent, and if n4 is an integer of 2 or more, the 2 or more X₄ groupsmay be the same or different, but n1 to n4 are not limited thereto.

For example, in Formulas 1 and 2, n1 to n4 may each be 1, but n1 to n4are not limited thereto.

According to an embodiment of the present invention, in Formula 1, Y₁ toY₄ may each independently be a substituted or unsubstituted C₃-C₁₀cycloalkyl group, a substituted or unsubstituted C₂-C₁₀ heterocycloalkylgroup, a substituted or unsubstituted C₂-C₁₀ cycloalkenyl group, asubstituted or unsubstituted C₂-C₁₀ heterocycloalkenyl group, asubstituted or unsubstituted C₆-C₃₀ aryl group, or a substituted orunsubstituted C₂-C₃₀ heteroaryl group.

For example, in Formula 1 above, Y₁ to Y₄ may each independently be asubstituted or unsubstituted phenyl group, a substituted orunsubstituted pentalenyl group, a substituted or unsubstituted indenylgroup, a substituted or unsubstituted naphthyl group, a substituted orunsubstituted azulenyl group, a substituted or unsubstituted heptalenylgroup, a substituted or unsubstituted indacenyl group, a substituted orunsubstituted acenaphthyl group, a substituted or unsubstitutedfluorenyl group, a substituted or unsubstituted phenalenyl group, asubstituted or unsubstituted phenanthrenyl group, a substituted orunsubstituted anthryl group, a substituted or unsubstitutedfluoranthenyl group, a substituted or unsubstituted triphenylenyl group,a substituted or unsubstituted pyrenyl group, a substituted orunsubstituted chrysenyl group, a substituted or unsubstitutednaphthacenyl group, a substituted or unsubstituted picenyl group, asubstituted or unsubstituted perylenyl group, a substituted orunsubstituted pentaphenyl group, a substituted or unsubstitutedhexacenyl group, a substituted or unsubstituted pyrrolyl group, asubstituted or unsubstituted imidazolyl group, a substituted orunsubstituted pyrazolyl group, a substituted or unsubstituted pyridinylgroup, a substituted or unsubstituted pyrazinyl group, a substituted orunsubstituted pyrimidinyl group, a substituted or unsubstitutedpyridazinyl group, a substituted or unsubstituted isoindolyl group, asubstituted or unsubstituted indolyl group, a substituted orunsubstituted indolyl group, a substituted or unsubstituted indazolylgroup, a substituted or unsubstituted purinyl group, a substituted orunsubstituted quinolinyl group, a substituted or unsubstitutedbenzoquinolinyl group, a substituted or unsubstituted phthalazinylgroup, a substituted or unsubstituted naphthyridinyl group, asubstituted or unsubstituted quinoxalinyl group, a substituted orunsubstituted quinazolinyl group, a substituted or unsubstitutedcinnolinyl group, a substituted or unsubstituted carbazolyl group, asubstituted or unsubstituted phenanthridinyl group, a substituted orunsubstituted acridinyl group, a substituted or unsubstitutedphenanthrolinyl group, a substituted or unsubstituted phenazinyl group,a substituted or unsubstituted benzoimidazolyl group, a substituted orunsubstituted furanyl group, a substituted or unsubstituted benzofuranylgroup, a substituted or unsubstituted thiophenyl group, a substituted orunsubstituted benzothiophenyl group, a substituted or unsubstitutedthiazolyl group, a substituted or unsubstituted isothiazolyl group, asubstituted or unsubstituted benzothiazolyl group, a substituted orunsubstituted isoxazolyl group, a substituted or unsubstituted oxazolylgroup, a substituted or unsubstituted triazolyl group, a substituted orunsubstituted tetrazolyl group, a substituted or unsubstitutedoxadiazolyl group, a substituted or unsubstituted triazinyl group, asubstituted or unsubstituted benzoxazolyl group, a substituted orunsubstituted dibenzopuranyl group, a substituted or unsubstituteddibenzothiophenyl group, or a substituted or unsubstitutedbenzocarbazolyl group, but Y₁ to Y₄ are not limited thereto.

For example, in Formula 1, Y₁ to Y₄ may each independently be i) aphenyl group, a naphthyl group, an anthracenyl group, or a fluorenylgroup; or ii) a phenyl group, a naphthyl group, an anthryl group, or afluorenyl group substituted with at least one of a deuterium atom, ahalogen atom, a hydroxyl group, a cyano group, a nitro group, an aminogroup, an amidino group, a hydrazine, a hydrazone, a carboxylic acidgroup or a salt thereof, a sulfonic acid group or a salt thereof, aphosphoric acid group or a salt thereof, or a C₁-C₁₀ alkyl group; aC₁-C₁₀ alkyl group substituted with at least one of a deuterium atom, ahalogen atom, a hydroxyl group, a cyano group, a nitro group, an aminogroup, an amidino group, a hydrazine, a hydrazone, a carboxylic acidgroup or a salt thereof, a sulfonic acid group or a salt thereof, aphosphoric acid group or a salt thereof, or a C₆-C₁₆ aryl group or aC₂-C₁₆ heteroaryl group; or a C₆-C₁₆ aryl group or a C₂-C₁₆ heteroarylgroup substituted with at least one of a deuterium atom, a halogen atom,a hydroxyl group, a cyano group, a nitro group, an amino group, anamidino group, a hydrazine, a hydrazone, a carboxylic acid group or asalt thereof, a sulfonic acid or a salt thereof, a phosphoric acid or asalt thereof, a C₁-C₆₀ alkyl group, a C₂-C₆₀ alkenyl group, a C₂-C₆₀alkynyl group, a C₁-C₆₀ alkoxy group, a C₆-C₁₆ aryl group, or a C₆-C₁₆aryl group, and a C₂-C₁₆ heteroaryl group, but Y₁ to Y₄ are not limitedthereto.

For example, in Formula 1, Y₁ to Y₄ may each independently be selectedfrom i) a phenyl group, a naphthyl group, or a fluorenyl group; ii) aphenyl group, a naphthyl group, or a fluorenyl group substituted with adeuterium atom, —F, a cyano group, a nitro group, a methyl group, anethyl group, an n-propyl group, an iso-propyl group, an n-butyl group,an iso-butyl group, or a tert-butyl group; iii) a phenyl group, anaphthyl group, an anthracenyl group, or a fluorenyl group substitutedwith at least one of a phenyl group, a naphthyl group, an anthracenylgroup, or a fluorenyl group; or iv) a phenyl group, a naphthyl group, ora fluorenyl group substituted with at least one of a deuterium atom, —F,a cyano group, a nitro group, a methyl group, an ethyl group, ann-propyl group, an iso-propyl group, an n-butyl group, an iso-butylgroup, a tert-butyl group, a phenyl group, a naphthyl group, ananthracenyl group, or a fluorenyl group, but Y₁ to Y₄ are not limitedthereto.

For example, in Formula 1, Y₁ to Y₄ may each independently be selectedfrom i) a phenyl group, a naphthyl group, or a fluorenyl group; ii) aphenyl group, a naphthyl group, or a fluorenyl group substituted with atleast one of a deuterium atom, —F, a cyano group, a nitro group, amethyl group, an ethyl group, an n-propyl group, an iso-propyl group, ann-butyl group, an iso-butyl group, or a tert-butyl group; or iii) aphenyl group, a naphthyl group, or a fluorenyl group substituted with atleast one of a phenyl group, a naphthyl group, an anthracenyl group, ora fluorenyl group, but Y₁ to Y₄ are not limited thereto.

For example, in Formula 1, Y₁ to Y₄ may each independently be at leastone group represented by one of Formulas 5a to 5f, but Y₁ to Y₄ are notlimited thereto:

In Formulas 5a to 5f, * is a bonding site to N, Z₁ or Z₂.

According to an embodiment of the present invention, in Formulas 1 and2, Z₁ and Z₂ may each independently be a substituted or unsubstitutedC₂-C₁₀ heterocycloalkyl group, a substituted or unsubstituted C₂-C₁₀heterocycloalkenyl group, or a substituted or unsubstituted C₂-C₆₀heteroaryl group, but Z₁ and Z₂ are not limited thereto.

For example, in Formula 2, Z₁ and Z₂ may independently be a substitutedor unsubstituted pyrrolyl group, a substituted or unsubstitutedimidazolyl group, a substituted or unsubstituted pyrazolyl group, asubstituted or unsubstituted triazolyl group, a substituted orunsubstituted pyridinyl group, a substituted or unsubstituted pyrazinylgroup, a substituted or unsubstituted pyrimidinyl group, a substitutedor unsubstituted pyridazinyl group, a substituted or unsubstitutedtriazinyl group, a substituted or unsubstituted isoindolyl group, asubstituted or unsubstituted indolyl group, a substituted orunsubstituted indazolyl group, a substituted or unsubstituted purinylgroup, a substituted or unsubstituted quinolinyl group, a substituted orunsubstituted benzoquinolinyl group, a substituted or unsubstitutedphthalazinyl group, a substituted or unsubstituted naphthyridinyl group,a substituted or unsubstituted quinoxalinyl group, a substituted orunsubstituted quinazolinyl group, a substituted or unsubstitutedcinnolinyl group, a substituted or unsubstituted carbazolyl group, asubstituted or unsubstituted phenanthridinyl group, a substituted orunsubstituted acridinyl group, a substituted or unsubstitutedphenanthrolinyl group, a substituted or unsubstituted phenazinyl group,a substituted or unsubstituted benzoimidazolyl group, a substituted orunsubstituted oxazolyl group, a substituted or unsubstituted isoxazolylgroup, a substituted or unsubstituted oxadiazolyl group, a substitutedor unsubstituted benzoxazolyl group, or a substituted or unsubstitutedbenzocarbazolyl group, but Z₁ and Z₂ are not limited thereto.

For example, in Formula 2, Z₁ and Z₂ may each independently be i) apyrrolyl group, an imidazolyl group, a triazolyl group, a pyridyl group,a triazinyl group, an isoindolyl group, an indolyl group, an indazolylgroup, a benzoimidazolyl group, an oxazolyl group, an isoxazolyl group,an oxadiazolyl group, or a benzoxazolyl group; or ii) a pyrrolyl group,an imidazolyl group, a triazolyl group, a pyridyl group, a triazinylgroup, an isoindolyl group, an indolyl group, an indazolyl group, abenzoimidazolyl group, an oxazolyl group, an isoxazolyl group, anoxadiazolyl group, or a benzoxazolyl group substituted with at least oneof a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, anitro group, an amino group, an amidino group, a hydrazine, a hydrazone,a carboxylic acid group or a salt thereof, a sulfonic acid group or asalt thereof, a phosphoric acid group or a salt thereof, or a C₁-C₁₀alkyl group; a C₆-C₁₆ aryl group or a C₂-C₁₆ heteroaryl group; or aC₆-C₁₆ aryl group or a C₂-C₁₆ heteroaryl group substituted with at leastone of a deuterium atom, a halogen atom, a hydroxyl group, a cyanogroup, a nitro group, an amino group, an amidino group, a hydrazine, ahydrazone, a carboxylic acid group or a salt thereof, a sulfonic acidgroup or a salt thereof, a phosphoric acid group or a salt thereof, aphosphoric acid group or a salt thereof, a C₁-C₆₀ alkyl group, a C₂-C₆₀alkenyl group, a C₂-C₆₀ alkynyl group, a C₁-C₆₀ alkoxy group, a C₆-C₁₆aryl group, or a C₂-C₁₆ heteroaryl group, but Z₁ and Z₂ are not limitedthereto.

For example, in Formula 2, Z₁ and Z₂ may each independently be i) atriazolyl group, a pyridyl group, a triazinyl group, a benzoimidazolylgroup, or an oxadiazolyl group; ii) a triazolyl group, a pyridyl group,a triazinyl group, a benzoimidazolyl group, or an oxadiazolyl groupsubstituted with at least one of a deuterium atom, —F, a cyano group, anitro group, a methyl group, an ethyl group, an n-propyl group, aniso-propyl group, an n-butyl group, an iso-butyl group, or a tert-butylgroup; iii) a triazolyl group, a pyridyl group, a triazinyl group, abenzoimidazolyl group, or an oxadiazolyl group substituted with at leastone of a phenyl group, a naphthyl group, an anthracenyl group, apyrrolyl group, an imidazolyl group, a pyrazolyl group, or a triazolylgroup; or iv) a triazolyl group, a pyridyl group, a triazinyl group, abenzoimidazolyl group, or an oxadiazolyl group substituted with at leastone of a phenyl group, a naphthyl group, an anthracenyl group, apyrrolyl group, an imidazolyl group, a pyrazolyl group, or a triazolylgroup substituted with at least one of a deuterium atom, —F, a cyanogroup, a nitro group, a methyl group, an ethyl group, an n-propyl group,an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butylgroup, a phenyl group, a naphthyl group, or an anthracenyl group, but Z₁and Z₂ are not limited thereto.

For example, in Formula 2, Z₁ and Z₂ may each independently be a grouprepresented by one of Formulas 3a to 3i, but Z₁ and Z₂ are not limitedthereto:

In Formulas 3a to 3i, R₃₁ to R₃₉ may each independently be a hydrogenatom, a deuterium atom, —F, a cyano group, a methyl group, an ethylgroup, a phenyl group, a biphenyl group, or a naphthyl group.

c1 to c8 may each independently be an integer of 0 to 4. If c1 is aninteger of 2 or more, the 2 or more R₃₁ groups may be the same ordifferent, if c2 is an integer of 2 or more, the 2 or more R₃₂ groupsmay be the same or different, if c3 is an integer of 2 or more, the 2 ormore R₃₃ groups may be the same or different, if c4 is an integer of 2or more, the 2 or more R₃₄ groups may be the same or different, if c5 isan integer of 2 or more, the 2 or more R₃₅ groups may be the same ordifferent, if c6 is an integer of 2 or more, the 2 or more R₃₅ groupsmay be the same or different, if c6 is an integer of 2 or more, the 2 ormore R₃₆ groups may be the same or different, if c7 is an integer of 2or more, the 2 or more R₃₇ groups may be the same or different, and ifc8 is an integer of 2 or more, the 2 or more R₃₈ groups may be the sameor different.

* is a bonding site to X₃ or X₄.

According to an embodiment of the present inventive concept, in Formulas1 and 2, R₁ to R₄ may each independently be selected from a deuteriumatom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, anamino group, an amidino group, a hydrazine, a hydrazone, a carboxylicadd group or a salt thereof, a sulfonic acid group or a salt thereof, aphosphoric acid group or a salt thereof, a phosphoric acid group or asalt thereof, a substituted or unsubstituted C₁-C₆₀ alkyl group, asubstituted or unsubstituted C₂-C₆₀ alkenyl group, a substituted orunsubstituted C₂-C₆₀ alkynyl group, a substituted or unsubstitutedC₁-C₆₀ alkoxy group, a substituted or unsubstituted C₃-C₁₀ cycloalkylgroup, a substituted or unsubstituted C₂-C₁₀ heterocycloalkyl group, asubstituted or unsubstituted C₃-C₁₀ cycloalkenyl group, a substituted orunsubstituted C₂-C₁₀ heterocycloalkenyl group, a substituted orunsubstituted C₆-C₆₀ aryl group, a substituted or unsubstituted C₆-C₆₀aryloxy group, a substituted or unsubstituted C₆-C₆₀ arylthio group, ora substituted or unsubstituted C₂-C₆₀ heteroaryl group, but R₁ to R₄ arenot limited thereto.

For example, in Formulas 1 and 2, R₁ to R₄ may each independently be ahydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, acyano group, a nitro group, and a C₁-C₁₀ alkyl group; or a C₁-C₁₀ alkylgroup substituted with at least one of a deuterium atom, a halogen atom,a hydroxyl group, a cyano group, a nitro group, an amino group, anamidino group, a hydrazine, a hydrazone, a carboxylic acid group or asalt thereof, a sulfonic acid group or a salt thereof, a phosphoric acidgroup or a salt thereof, a phosphoric acid group or a salt thereof; aC₆-C₁₆ aryl group; or a C₆-C₁₆ aryl group substituted with at least oneof a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, anitro group, an amino group, an amidino group, a hydrazine, a hydrazone,a carboxylic acid group or a salt thereof, a sulfonic acid group or asalt thereof, a phosphoric acid group or a salt thereof, a phosphoricacid group or a salt thereof, a C₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxygroup, a phenyl group, a naphthyl group, or an anthryl group, but R₁ toR₄ are not limited thereto.

For example, in Formulas 1 and 2, R₁ to R₄ may each independently be ahydrogen atom, a deuterium atom, an —F, a nitro group, a methyl group,an ethyl group, an n-propyl group, an iso-propyl group, an n-butylgroup, an iso-butyl group, or a tert-butyl group; a methyl group, anethyl group, an n-propyl group, an iso-propyl group, an n-butyl group,an iso-butyl group, or a tert-butyl group substituted with at least oneof a hydrogen atom, a deuterium atom, —F, a cyano group, a nitro group,a methyl group, an ethyl group, an n-propyl group, an iso-propyl group,an n-butyl group, an iso-butyl group, or a tert-butyl group; or a phenylgroup, a naphthyl group, or an anthracenyl group substituted with atleast one of a hydrogen atom, a deuterium atom, —F, a cyano group, anitro group, a methyl group, an ethyl group, an n-propyl group, aniso-propyl group, an n-butyl group, an iso-butyl group, or a tert-butylgroup, but R₁ to R₄ are not limited thereto.

For example, in Formulas 1 and 2, R₁ to R₄ may be the same, but are notlimited thereto. In one embodiment, for example, R₁ to R₄ may all behydrogen atoms.

According to an embodiment of the present inventive concept, in Formulas1 and 2, a1 to a4 each independently represent numbers each of R₁ to R₄,a1 to a4 are each independently an integer of 0 to 4, and if a1 is aninteger of 2 or more, then 2 or more of R₁ may be the same or different,if a2 is an integer of 2 or more, then 2 or more of R₂ may be the sameor different, if a3 is a an integer of 2 or more, then 2 or more of R₃may be the same or different, and if a4 is an integer of 2 or more, then2 or more of R₄ may be the same or different, but not limited thereto.

For example, in Formula 1, a1 may be 0, but is not limited thereto.

For example, in Formula 1, a2 may be 0, but is not limited thereto.

For example, in Formula 1, a1 may be 0 and a2 may be 0, but a1 and a2are not limited thereto. Here, if a1 and a2 are both 0, the pyrene ringis not substituted.

For example, in Formula 2, a3 may be 0, but is not limited thereto.

For example, in Formula 2, a4 may be 0, but is not limited thereto.

For example, in Formula 2, a3 may be 0 and a4 may be 0, but a3 and a4are not limited thereto. Here, if a3 and a4 are both 0, the pyrene ringis not substituted.

According to an embodiment of the present invention, in Formulas 1 and2, b1 represents the number of moieties represented by

(where * is a linking site to a pyrene ring), and b2 represents thenumber of moieties represented by

(where * is a linking site to a pyrene ring). b1 and b2 may eachindependently be an integer 0 or 1, but b1 and b2 are not limitedthereto.

For example, in Formulas 1 and 2, b1 and b2 may each independently be 0,but b1 and b2 are not limited thereto.

According to an embodiment of the present invention, the amine-basedcompound may be represented by Formula 1a below, but is not limitedthereto.

In Formula 1a, X₁ may be a phenylene group or a naphthylene group; or aphenylene group or a naphthylene group substituted with at least one ofa deuterium atom, —F, a cyano group, a nitro group, a methyl group, anethyl group, an n-propyl group, an iso-propyl group, an n-butyl group,an iso-butyl group, or a tert-butyl group.

Y₁ and Y₂ may each independently be i) a phenyl group, a naphthyl group,or a fluorenyl group; ii) a phenyl group, a naphthyl group, or afluorenyl group substituted with at least one of a deuterium atom, —F, acyano group, a nitro group, a methyl group, an ethyl group, an n-propylgroup, an iso-propyl group, an n-butyl group, an iso-butyl group, or atert-butyl group; or iii) a phenyl group, a naphthyl group, or afluorenyl group substituted with at least one of a phenyl group, anaphthyl group, an anthracenyl group, or a fluorenyl group.

According to an embodiment of the present invention, the pyrene-basedcompound may be represented by Formula 2a below, but is not limitedthereto.

In Formula 2a, X₃ may be a phenylene group or a naphthylene group; or aphenylene group or a naphthylene group substituted with at least one ofa deuterium atom ion, —F, a cyano group, a nitro group, a methyl group,an ethyl group, an n-propyl group, an iso-propyl group, an n-butylgroup, an iso-butyl group, or a tert-butyl group.

Z₁ and Z₂ may be each independently at least one group represented byone of Formulas 3a to 3i below, but Z₁ and Z₂ are not limited thereto:

In Formulas 3a to 3i, R₃₁ to R₃₉ may each independently be a hydrogenatom, a deuterium atom, —F, a cyano group, a nitro group, a methylgroup, an ethyl group, a phenyl group, a biphenyl group, or a naphthylgroup.

c1 to c5 may each independently an integer of 0 to 4. If c1 is aninteger of 2 or more, the 2 or more R₃₁ groups may be the same ordifferent, if c2 is an integer of 2 or more, the 2 or more R₃₂ groupsmay be the same or different, if c3 is an integer of 2 or more, the 2 ormore R₃₃ groups may be the same or different, if c4 is an integer of 2or more, the 2 or more R₃₄ groups may be the same or different, if c5 isan integer of 2 or more, the 2 or more R₃₅ groups may be the same ordifferent, if c6 is an integer of 2 or more, the 2 or more R₃₆ groupsmay be the same or different, if c7 is an integer of 2 or more, the 2 ormore R₃₇ groups may be the same or different, and if c8 is an integer of2 or more, the 2 or more R₃₈ groups may be the same or different.

* is a bonding site to X₃ or X₄.

According to an embodiment of the present invention, the amine-basedcompound may be represented by Formula 1a below, and the pyrene-basedcompound may be represented by Formula 2a below, but the amine-basedcompound and pyrene-based compound are not limited thereto:

In Formula 1a, X₁ may be a phenylene group or a naphthylene group; or aphenylene group or a naphthylene group substituted with at least one ofa deuterium atom ion, —F, a cyano group, a nitro group, a methyl group,an ethyl group, an n-propyl group, an iso-propyl group, an n-butylgroup, an iso-butyl group, or a tert-butyl group.

Y₁ and Y₂ may each independently be at least one of i) a phenyl group, anaphthyl group, or a fluorenyl group; ii) a phenyl group, a naphthylgroup, or a fluorenyl group substituted with at least one of a deuteriumatom ion, —F, a cyano group, a nitro group, a methyl group, an ethylgroup, an n-propyl group, an iso-propyl group, an n-butyl group, aniso-butyl group, or a tert-butyl group; or iii) a phenyl group, anaphthyl group, or a fluorenyl group substituted with at least one of aphenyl group, a naphthyl group, an anthracenyl group, or a fluorenylgroup.

In Formula 2a, X₃ may be a phenylene group or a naphthylene group; or aphenylene group or a naphthylene group substituted with at least one ofa deuterium atom ion, —F, a cyano group, a nitro group, a methyl group,an ethyl group, an n-propyl group, an iso-propyl group, an n-butylgroup, an iso-butyl group, or a tert-butyl group.

Z₁ may be at least one group represented by one of Formulas 3a to 3ibelow, but Z₁ is not limited thereto.

In Formulas 3a to 3i, R₃₁ to R₃₉ may each independently be a hydrogenatom, a deuterium atom, —F, a cyano group, a nitro group, a methylgroup, an ethyl group, a phenyl group, a biphenyl group, or a naphthylgroup.

c1 to c8 may each independently be an integer of 0 to 4. If c1 is aninteger of 2 or more, the 2 or more R₃₁ groups may be the same ordifferent, if c2 is an integer of 2 or more, the 2 or more R₃₂ groupsmay be the same or different, if c3 is an integer of 2 or more, the 2 ormore R₃₃ groups may be the same or different, if c4 is an integer of 2or more, the 2 or more R₃₄ groups may be the same or different, if c5 isan integer of 2 or more, the 2 or more R₃₅ groups may be the same ordifferent, if c6 is an integer of 2 or more, the 2 or more R₃₆ groupsmay be the same or different, if c7 is an integer of 2 or more, the 2 ormore R₃₇ groups may be the same or different, and if c8 is an integer of2 or more, the 2 or more R₃₅ groups may be the same or different.

* may be a bonding site to X₃ or X₄, but not limited thereto.

According to embodiments of the present invention, the amine-basedcompound may be at least one of Compounds 1 to 14 below, but theamine-based compound is not limited thereto.

According to embodiments of the present invention, the pyrene-basedcompound may be at least one of Compounds 15 to 21 below, but thepyrene-based compound is not limited thereto:

According to embodiments of the present invention, the amine-basedcompound may be one of Compounds 1 to 14 below, and the pyrene-basedcompound may be one of Compounds 15 to 21, but the amine-based compoundand the pyrene-based compound are not limited thereto.

The amine-based compound represented by Formula 1 is a material havinggood hole transport ability. Also, the pyrene-based compound representedby Formula 2 is a material having good electron transport ability.Accordingly, by using both an amine-based compound having good holetransport ability and a pyrene-based compound having good electrontransport ability in an organic layer, holes and electrons aresufficiently supplied in the organic layer, thus improving efficiency.Also, the emission layer has both hole affinity and electron affinity,thereby substantially preventing sharp reductions in lifespan caused bya predominance of one of the carriers in the emission layer.

The organic layer includes a hole transport region between the firstelectrode and the emission layer, and has at least one of a holeinjection layer, a hole transport layer, a functional layer having bothhole injection ability and hole transport ability (hereinafter referredto as an ‘H-functional layer’), a buffer layer, and/or an electronblocking layer. The organic layer also has an electron transport regionbetween the emission layer and the second electrode, and has at leastone of a hole blocking layer, an electron transport layer, and/or anelectron injection layer.

According to an embodiment of the present invention, the amine-basedcompound and the pyrene-based compound may be included in the emissionlayer, but the present invention is not limited thereto.

For example, the amine-based compound and the pyrene-based compound maybe co-deposited, but the present invention is not limited thereto.

For example, the amine-based compound and the pyrene-based compound maybe co-deposited in a weight ratio of about 3:1 to about 1:3, but thepresent invention is not limited thereto. When the ratio ofco-deposition is within this range, the organic light-emitting diode mayhave higher efficiency.

For example, the emission layer may include a first emission layer and asecond emission layer, and the first emission layer may include theamine-based compound, and the second emission layer may include thepyrene-based compound, but the present invention is not limited thereto.

For example, the first emission layer may be disposed between the secondemission layer and the first electrode, but the present invention is notlimited thereto.

FIG. 1 is a schematic view of an organic light-emitting diode 10according to an embodiment of the present invention. Hereinafter, astructure and a method of manufacturing the organic light-emittingdiode, according to an embodiment of the present invention, will bedescribed with reference to FIG. 1.

A substrate 11 may be any substrate conventionally used in organiclight-emitting devices. In some embodiments, the substrate 11 may be aglass substrate or a transparent plastic substrate with good mechanicalstrength, thermal stability, transparency, surface smoothness, ease ofhandling, and water resistance.

A first electrode 13 may be formed by depositing or sputtering a firstelectrode-forming material onto a surface of the substrate 11. When thefirst electrode 13 is an anode, a material having a high work functionmay be used as the first electrode-forming material to facilitate holeinjection. The first electrode 13 may be a reflective electrode or atransmission electrode. Transparent and conductive materials such asITO, IZO, SnO₂, and ZnO may be used to form the first electrode 13. Thefirst electrode 13 may be formed as a reflective electrode usingmagnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca),magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), or the like.

The first electrode 13 may have a single-layer structure or amulti-layer structure including at least two layers. For example, thefirst electrode 13 may have a three-layered structure of ITO/Ag/ITO, butis not limited thereto.

An organic layer 15 may be disposed on the first electrode 13.

The organic layer 15 may include a hole injection layer (HIL), a holetransport layer (HTL), a buffer layer, an emission layer (EML), anelectron transport layer (ETL), and an electron injection layer (EIL).

The HIL may be formed on the first electrode 13 by vacuum deposition,spin coating, casting, Langmuir-Blodgett (LB) deposition, or the like.When the HIL is formed using vacuum deposition, the vacuum depositionconditions may vary depending on the compound used to form the HIL, andthe desired structure and thermal properties of the HIL to be formed.For example, vacuum deposition may be performed at a temperature ofabout 100° C. to about 500° C., a pressure of about 10⁻⁸ torr to about10⁻³ torr, and a deposition rate of about 0.01 Å/sec to about 100 Å/sec.However, the deposition conditions are not limited thereto.

When the HIL is formed using spin coating, the coating conditions mayvary according to the compound that is used to form the HIL, and thedesired structure and thermal properties of the HIL to be formed. Forexample, the coating rate may be in a range of about 2000 rpm to about5000 rpm, and a temperature at which heat treatment is performed toremove solvent after coating may be in a range of about 80° C. to about200° C. However, the coating conditions are not limited thereto.

The HIL may be formed of any material that is commonly used to form anHIL. Non-limiting examples of the material that may be used to form theHIL areN,N′-diphenyl-N,N′-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4′-diamine,(DNTPD), a phthalocyanine compound such as copper phthalocyanine,4,4′,4″-tris (3-methylphenylphenylamino)triphenylamine (m-MTDATA),N,N′-di(1-naphthyl-N,N′-diphenylbenzidine (NPB), TDATA, 2T-NATA,polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA),poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS),polyaniline/camphor sulfonic acid (Pani/CSA), andpolyaniline)/poly(4-styrenesulfonate (PANI/PSS), but not limitedthereto.

Alternatively, the HIL may include at least one type of silicon-basedcompound.

The thickness of the HIL may be about 100 Å to about 10000 Å, and insome embodiments, may be from about 100 Å to about 1000 Å. When thethickness of the HIL is within these ranges, the HIL may have good holeinjecting ability without a substantial increase in driving voltage.

Then, an HTL may be formed on the HIL by vacuum deposition, spincoating, casting, LB deposition, or the like. When the HTL is formedusing vacuum deposition or spin coating, the conditions for depositionor coating may be similar to those for the formation of the HIL, thoughthe conditions for the deposition or coating may vary depending on thecompound used to form the HTL.

Non-limiting examples of suitable known HTL forming materials includecarbazole derivatives, such as N-phenylcarbazole or polyvinylcarbazole,N,N′-bis(3-methylphenyl-N,N′-diphenyl-[1,1-biphenyl]-4,4′-diamine (TPD),4,4′,4″-tris(N-carbazolyl triphenylamine (TCTA), andN,N′-di(1-naphthyl-N,N′-diphenylbenzidine) (NPB). Alternatively, the HTLmay include at least one type of silicon-based compound.

The thickness of the HTL may be from about 50 Å to about 2000 Å, and insome embodiments, may be from about 100 Å to about 1500 Å. When thethickness of the HTL is within these ranges, the HTL may have good holetransporting ability without a substantial increase in driving voltage.

The H-functional layer (having both hole injection and hole transportcapabilities) may include at least one hole injecting material and atleast one hole transporting material. A thickness of the H-functionallayer may be in a range of about 500 Å to about 10,000 Å, for example,about 100 Å to about 1,000 Å. When the thickness of the H-functionallayer is within the above ranges, the H-functional layer may have goodhole injection and transport capabilities without a substantial increasein driving voltage.

In some embodiments, in addition to the known hole injecting material,the known hole transporting material, and/or the material simultaneouslyhaving hole injection and transport capabilities described above, atleast one of the HIL, HTL, and H-functional layer may further include anelectric charge-generating material for improving conductivity of thelayer.

Examples of the electric charge-generating material include quininederivatives, metal oxides, and cyano compounds, but are not limitedthereto. For example, non-limiting examples of the electriccharge-generating compound include quinine derivatives such astetracyanoquinodimethane (TCNQ) and2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinodimethane (F4-TCNQ); metaloxides such as tungsten oxide and molybdenum oxide; and cyano compoundssuch as compound 200 below.

When the HIL, HTL, or H-functional layer further includes an electriccharge-generating material, the electric charge-generating material maybe included in any manner, such as being homogeneously dispersed orirregularly distributed in the HIL, HTL, or H-functional layer.

A buffer layer may be disposed between the EML and at least one of theHIL, HTL, and H-functional layer. The buffer layer may compensate for anoptical resonance distance of light according to a wavelength of thelight emitted from the EML, and thus may increase efficiency. The bufferlayer may include any hole injecting material or hole transportingmaterial. In some other embodiments, the buffer layer may include thesame material as one of the materials included in the HIL, HTL, andH-functional layer that underlies the buffer layer.

Then, an EML may be formed on the HTL, H-functional layer, or bufferlayer by vacuum deposition, spin coating, casting, LB deposition, or thelike. When the EML is formed using vacuum deposition or spin coating,the deposition or coating conditions may be similar to those used toform the HIL, though the conditions for deposition and coating may varydepending on the compound used to form the EML.

The EML may include a known light-emitting material. For example, theEML may include a known host and a known dopant.

Nonlimiting examples of the host include Alq₃, CBP(4,4′-N,N′-dicarbazole-biphenyl), PVK (poly(n-vinylcarbazole)),9,10-di(naphthylene-2-yl)anthracene (DNA), TCTA, TPBI(1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene), TBADN(3-tert-butyl-9,10-di(naphth-2-yl) anthracene), mCP, OXD-7, or the like.

The dopant may be at least one or a fluorescent dopant or aphosphorescent dopant. The phosphorescent dopant may be an organic metalcomplex including a composite of at least two of Ir, Pt, Os, Re, Ti, Zr,Hf, or a combination thereof, but not limited thereto.

Examples of blue dopants include F₂Irpic, (F₂ppy)₂Ir(tmd), Ir(dfppz)₃,ter-fluorene, 4,4′-bis(4-diphenylaminostyryl)biphenyl (DPAVBi),2,5,8,11-tetra-tert-butyl pherylene (TBPe), DPVBi, but are not limitedthereto.

Examples of red dopants include PtOEP, Ir(piq)₃, Btplr, or the like, butare not limited thereto.

Examples of green dopants include Ir(ppy)₃ (ppy=phenylpyridine),Ir(ppy)₂(acac), Ir(mpyp)₃, or the like, but are not limited thereto.

When the EML includes both a host and a dopant, the amount of the dopantmay be from about 0.01 to about 15 parts by weight based on 100 parts byweight of the host. However, the amount of the dopant is not limited tothis range.

The thickness of the EML may be about 200 Å to about 700 Å. When thethickness of the EML is within these ranges, the EML may have goodlight-emitting ability without a substantial increase in drivingvoltage.

Then, an ETL may be formed on the EML or a hole blocking layer (HBL) byany of a variety of methods, for example, vacuum deposition, spincoating, or casting. When the ETL is formed using vacuum deposition orspin coating, the deposition or coating conditions may be similar tothose used to form the HIL, though the deposition or coating conditionsmay vary depending on the compound used to form the ETL.

Any known electron transporting material that can stably transportelectrons injected from an electron injecting electrode (cathode) may beused as the material for the ETL. Non-limiting examples of materials forforming the ETL include a quinoline derivative, such astris(8-quinolinorate)aluminum (Alq3), TAZ, BAlq, berylliumbis(benzoquinolin-10-olate (Bebq2), 9,10-di(naphthylene-2-yl)anthracene(ADN), Compound 101, Compound 102, Bphen, or the like.

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A thickness of the ETL may be from about 100 Å to about 1,000 Å, and insome embodiments, may be from about 150 Å to about 500 Å. When thethickness of the ETL is within these ranges, the ETL may havesatisfactory electron transporting ability without a substantialincrease in driving voltage.

In some embodiments, the ETL may further include a metal-containingmaterial in addition to the electron-transporting organic compound. Themetal-containing material may include a lithium (Li) complex.Non-limiting examples of the Li complex may be lithium quinolate (LiQ)or Compound 203 below.

Then, an EIL, which facilitates injection of electrons from the cathode,may be formed on the ETL. Any suitable electron-injecting material maybe used to form the EIL.

Non-limiting examples of the material for forming the EIL include LiF,NaCl, CsF, Li₂O, and BaO. The deposition or coating conditions forforming the EIL may be similar to those for the formation of the HIL,though the deposition or coating conditions may vary according to thematerial used to form the EIL.

A thickness of the EIL may be from about 1 Å to about 100 Å, and in someembodiments, may be from about 3 Å to about 90 Å. When the thickness ofthe EIL is within these ranges, the EIL may have satisfactory electroninjection ability without a substantial increase in driving voltage.

A second electrode 17 may be disposed on the organic layer 15. Thesecond electrode 17 may be a cathode, which is an electron injectionelectrode. Here, the second electrode-forming material may be a metal,an alloy, an electro-conductive compound (which are materials having alow work function), or a mixture thereof. In this regard, the secondelectrode 16 may be formed as a transmission electrode using lithium(Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium(Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), or the like.In some embodiments, in order to manufacture a top-emissionlight-emitting diode, the transmission electrode may be formed of indiumtin oxide (ITO) or indium zinc oxide (IZO).

Also, when a phosphorescent dopant is used in the EML, an HBL may beformed between the HTL and the EML, or between the H-functional layerand the EML to prevent triplet excitons or holes from dispersing intothe electron transport layer. The HBL may be deposited by vacuumdeposition, spin coating, casting, LB deposition, or the like. When theHIL is formed by vacuum deposition or spin coating, the deposition orcoating conditions may be similar to those used to form the HIL, thoughthe conditions for deposition or coating may vary depending on thecompound used to form the HIL. A known hole blocking material may alsobe used, and examples thereof include an oxadiazole derivative, atriazole derivative, a phenanthroline derivative, or the like. Forexample, BCP may be used as the hole blocking material.

A thickness of the HBL may be from about 20 Å to about 1000 Å, and insome embodiments, may be from about 30 Å to about 300 Å. When thethickness of the EIL is within these ranges, the EIL may havesatisfactory hole blocking ability without a substantial increase indriving voltage.

Although the organic light-emitting device 10 of FIG. 1 is describedabove, the present invention is not limited thereto.

The unsubstituted C₁-C₆₀ alkyl group refers to linear or a branchedalkyl group having from 1 to 60 carbon atoms, for example, methyl,ethyl, propyl, isobutyl, sec-butyl, pentyl, isoamyl, hexyl, and thelike. The substituted C₁-C₆₀ alkyl group refers to the substitution ofat least one hydrogen atom of the unsubstituted C₁-C₆₀ alkyl group withat least one of a deuterium atom, a halogen atom, a hydroxyl group, acyano group, a nitro group, an amino group, an amidino group, ahydrazine, a hydrazone, a carboxylic acid group or a salt thereof, asulfonic acid group or a salt thereof, a phosphoric acid group or a saltthereof, a C₁-C₆₀ alkyl group, a C₁-C₆₀ alkenyl group, a C₂-C₆₀ alkynylgroup, a C₁-C₆₀ alkoxy group; a C₃-C₁₀ cycloalkyl group, a C₂-C₁₀heterocycloalkyl group, a C₃-C₁₀ cycloalkenyl group, a C₂-C₁₀heterocycloalkenyl group, a C₆-C₆₀ aryl group, a C₆-C₆₀ aryloxy group, aC₆-C₆₀ arylthio group, or a C₂-C₆₀ heteroaryl group substituted with atleast one of a deuterium atom, a halogen atom, a hydroxyl group, a cyanogroup, a nitro group, an amino group, an amidino group, a hydrazine, ahydrazone, a carboxylic acid group or a salt thereof, a sulfonic acidgroup or a salt thereof, or a phosphoric acid group or a salt thereof; aC₃-C₁₀ cycloalkyl group, a C₂-C₁₀ heterocycloalkyl group, a C₃-C₁₀cycloalkenyl group, a C₂-C₁₀ heterocycloalkenyl group, a C₆-C₆₀ arylgroup, a C₆-C₆₀ aryloxy group, a C₆-C₆₀ arylthio group, or a C₂-C₆₀heteroaryl group substituted with at least one of a deuterium atom, ahalogen atom, a hydroxyl group, a cyano group, a nitro group, an aminogroup, an amidino group, a hydrazine, a hydrazone, a carboxylic acidgroup or a salt thereof, a sulfonic acid group or a salt thereof, aphosphoric acid group or a salt thereof, a C₁-C₆₀ alkyl group, a C₂-C₆₀alkenyl group, a C₂-C₆₀ alkynyl group, a C₁-C₆₀ alkoxy group, a phenylgroup, a naphthyl group, an anthryl group, a fluorenyl group, adimethylfluorenyl group, a diphenyl fluorenyl group, a carbazolyl group,a phenylcarbazolyl group, a pyridyl group, a pyrimidyl group, apyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolylgroup, or an isoquinolyl group; or —N(Q₁₁)(Q₁₂); or —Si(Q₁₃)(Q₁₄)(Q₁₅)(where Q₁₁ and Q₁₂ are each independently a C₁-C₆₀ alkyl group, a C₁-C₆₀alkoxy group, a C₆-C₆₀ aryl group, or a C₂-C₆₀ heteroaryl group).

In the present specification, the unsubstituted C₁-C₆₀ alkoxy group (orC₁-C₆₀ alkoxy group) is represented by —OA where A is an unsubstitutedC₁-C₆₀ alkyl group as described above. Examples of the unsubstitutedC₁-C₆₀ alkoxy group include a methoxy, an ethoxy, an isopropyloxy, orthe like. The substituted C₁-C₆₀ alkoxy group refers to the substitutionof at least one hydrogen atom of the alkoxy group with the substituentsdescribed above in connection with the substituted C₁-C₆₀ alkyl group.

In the present specification, the unsubstituted C₂-C₆₀ alkenyl group (orC₂-C₆₀ alkenyl group) refers to a group including at least onecarbon-carbon double bond in the middle or at the end of theunsubstituted C₂-C₆₀ alkenyl group. Examples thereof include an ethenyl,a propenyl, a butenyl, or the like. The substituted C₂-C₆₀ alkenyl grouprefers to the substitution of at least one hydrogen atom of the C₂-C₆₀alkenyl group with the substituents described above in connection withthe substituted C₁-C₆₀ alkyl group.

In the present specification, the unsubstituted C₂-C₆₀ alkynyl group (orC₂-C₆₀ alkynyl group) refers to a group including at least onecarbon-carbon triple bond in the middle or at the end of the C₂-C₆₀alkynyl group. Examples thereof include an ethynyl, a propenyl, or thelike. The substituted C₂-C₆₀ alkynyl group refers to the substitution ofat least one hydrogen atom of the C₂-C₆₀ alkynyl group with thesubstituents described above in connection with the substituted C₁-C₆₀alkyl group.

In the present specification, the unsubstituted C₃-C₃₀ cycloalkyl grouprefers to a cyclic saturated monovalent hydrocarbon having from 3 to 60carbon atoms. Examples thereof include a cyclopropyl, a cyclobutyl, acyclopentyl, a cyclohexyl, a cyclooctyl, or the like. The substitutedC₃-C₃₀ cycloalkyl group refers to the substitution of at least onehydrogen atom of the cycloalkyl group with the substituents describedabove in connection with the substituted C₁-C₆₀ alkyl group.

The unsubstituted C₃-C₃₀ cycloalkenyl group refers to a group having atleast one carbon-carbon double bond and an unsaturated hydrocarbon ringthat is not an aromatic ring. Examples of the unsubstituted C₃-C₃₀cycloalkenyl group include a cyclopropenyl, a cyclobutenyl, acyclopentenyl, a cyclohexenyl, a cycloheptenyl, a 1,3-cyclohexadienylgroup, a 1,4-cyclohexadienyl group, a 2,4-cycloheptadienyl group, a1,5-cyclooctadienyl group, or the like. The substituted C₃-C₃₀cycloalkenyl group refers to the substitution of at least one hydrogenatom of the cycloalkenyl group with the substituents described above inconnection with the substituted C₁-C₆₀ alkyl group.

The unsubstituted C₆-C₆₀ aryl group refers to a monovalent group havinga carbocyclic aromatic system having 6 to 60 carbon atoms including atleast one aromatic ring. The unsubstituted C₆-C₆₀ arylene group refersto a divalent group having a carbocyclic aromatic system having 6 to 60carbon atoms including at least one aromatic ring. When the aryl groupand the arylene group have at least two rings, they may be fused to eachother. The substituted C₆-C₆₀ aryl group and C₆-C₆₀ arylene group referto the substitution of at least one hydrogen atom of the aryl group orthe arylene group with the substituents described above in connectionwith the C₁-C₆₀ alkyl group.

Examples of the substituted or unsubstituted C₆-C₆₀ aryl group include aphenyl group, a C₁-C₁₀ alkylphenyl group (e.g., an ethylphenyl group), aC₁-C₁₀ alkylbiphenyl group (e.g., an ethylbiphenyl group), a halophenylgroup (e.g., an o-, m- or p-fluorophenyl group or a dichlorophenylgroup), a dicyanophenyl group, a trifluoromethoxyphenyl group, an o-, m-or p-tolyl group, an o-, m- or p-cumenyl group, a mesityl group, aphenoxyphenyl group, an (α,α-dimethylbenzene)phenyl group, an(N,N′-dimethyl)aminophenyl group, an (N,N′-diphenyl)aminophenyl group, apentalenyl group, an indenyl group, a naphthyl group, a halonaphthylgroup (e.g., a fluoronaphthyl group), a C₁-C₁₀ alkylnaphthyl group(e.g., a methylnaphthyl group), a C₁-C₁₀ alkoxynaphthyl group (e.g., amethoxynaphthyl group), an anthracenyl group, an azulenyl group, aheptalenyl group, an acenaphthylenyl group, a phenalenyl group, afluorenyl group, an anthraquinolyl group, a methylanthryl group, aphenanthryl group, a triphenylenyl group, a pyrenyl group, a chrysenylgroup, an ethyl-chrysenyl group, a picenyl group, a perylenyl group, achloroperylenyl group, a pentaphenyl group, a pentacenyl group, atetraphenylenyl group, a hexaphenyl group, a hexacenyl group, arubicenyl group, a coronenyl group, a trinaphthylenyl group, aheptaphenyl group, a heptacenyl group, a pyranthrenyl group, and anovalenyl group. Examples of the substituted C₆-C₆₀ aryl group may beinferred from the examples of the unsubstituted C₆-C₆₀ aryl group andthe substituted C₁-C₆₀ alkyl group described above. Examples of thesubstituted and unsubstituted C₆-C₆₀ arylene group may be inferred fromthe examples of the substituted and unsubstituted C₆-C₆₀ aryl groupdescribed above.

The unsubstituted C₂-C₆₀ heteroaryl group refers to a monovalent grouphaving at least one aromatic ring having at least one heteroatomselected from N, O, P, and S. The unsubstituted C₂-C₆₀ heteroarylenegroup may be a divalent group having at least one aromatic ring havingat least one heteroatom selected from N, O, P, and S. Here, when theheteroaryl group or the heteroarylene group has at least two rings, theymay be fused to each other. The substituted C₂-C₆₀ heteroaryl group andC₂-C₆₀ heteroarylene group refer to the substitution of at least onehydrogen atom of the heteroaryl group or the heteroarylene group withthe substituents described with reference to the C₁-C₆₀ alkyl group.

Examples of the unsubstituted C₂-C₆₀ heteroaryl group include apyrazolyl group, an imidazolyl group, an oxazolyl group, a thiazolylgroup, a triazolyl group, a tetrazolyl group, an oxadiazolyl group, apyridinyl group, a pyridazinyl group, a pyrimidyl group, a triazinylgroup, a carbazolyl group, an indolyl group, a quinolinyl group, anisoquinolinyl group, a benzoimidazolyl group, an imidazopyridinyl group,an imidazopyrimidyl group, or the like. Examples of the substituted orunsubstituted C₆-C₆₀ arylene group may be inferred from the examples ofthe substituted or unsubstituted C₂-C₆₀ arylene group described above.

The substituted or unsubstituted C₆-C₆₀ aryloxy group refers to a grouprepresented by —OA₂ where A₂ is a substituted or unsubstituted C₆-C₆₀aryl group described above. The substituted or unsubstituted C₆-C₆₀arylthio group refers to a group represented by —SA₃ where A₃ is asubstituted or unsubstituted C₆-C₆₀ aryl group described above.

Hereinafter, the present invention will be described with reference tothe following synthesis examples and other examples. However, theseexamples are presented for illustrative purposes only and are notintended to limit the scope of the present invention.

Example Synthesis Example 1 Synthesis of Compound 1

Compound 1 was synthesized according to Reaction Scheme 1 below:

A mixture of pyrene-1-boronic acid (0.75 g, 3.1 mmol), 4-bromo triphenylamine (1 g, 3.1 mmol), 2M potassium carbonate 16 ml, and Pd(PPh₃)₄ (0.15g, 0.09 mmol) in dimethoxy ethanol was refluxed under inert atmospherefor 15 h. After cooling at room temperature, the solvent was evaporatedin vacuum and the residue was dissolved in dimethylchloride. The organicphase was washed with distilled water, and moisture was removed bydrying with Na₂SO₄. The solvent was removed to obtain a crude product.The crude product was then subjected to column chromatography usingdimethyl chloride, ethyl acetate, and methanol as eluents to obtainCompound 1 (1.19 g, yield rate 85%). Compound 1 was observed through ¹HNMR, ¹³C NMR, MALDI-TOF MS, and HRMS (FAB).

¹H NMR (300 MHz, DMSO-d6): δ=(ppm) 8.32 (q, 6 Hz, 4H), 8.21 (q, 3 Hz,4H), 8.11-8.02 (m, 2H), 7.53 (d, 9 Hz 2H), 7.38 (t, 6 Hz, 4H), 7.19-7.08(m, 7H).

¹³C NMR (125 MHz, DMSO): δ=(ppm) 147.08, 146.66, 136.74, 134.02, 131.34,130.98, 130.43, 129.90, 129.67, 127.63, 127.57, 127.36. 127.27, 126.37,125.25, 124.96, 124.88, 124.71, 124.36, 124.23, 124.09, 123.99, 123.37,122.67

MALDI-TOF MS: C₃₄H₂₃N, estimated value 445.18 g/mol, measured value445.27 g/mol.

HRMS (FAB): C₃₄H₂₃N, estimated value 445.1830 g/mol, measured value445.1833 g/mol.

Synthesis Example 2 Synthesis of Compound 15

Compound 15 was synthesized according to Reaction Scheme 1 below:

A mixture of pyrene-1-boronic acid (0.8 g, 3.3 mmol),2-(4-Bromo-phenyl)-5-phenyl-[1,3,4]oxadiazole (1 g, 3.3 mmol), 2Mpotassium carbonate 20 ml, and Pd(PPh₃)₄ (0.156 g, 0.1 mmol) indimethoxy ethanol was refluxed under an inert atmosphere for 15 h. Aftercooling at room temperature, the solvent was evaporated in vacuum andthe residue was dissolved in dimethylchloride. The organic phase waswashed with distilled water, and moisture was removed by drying withNa₂SO₄. The solvent was removed to obtain a crude product. The crudeproduct was then subjected to column chromatography using dimethylchloride, ethyl acetate, and methanol as eluents to obtain Compound 15(1.14 g, yield rate 81%). Compound 15 was observed through ¹H NMR, ¹³CNMR, MALDI-TOF MS, and HRMS (FAB).

¹H NMR (300 MHz, DMSO-d6): δ=(ppm) 7.97 (d, 6 Hz, 2H), 7.84 (q, 6 Hz,2H), 7.76-7.73 (m, 2H), 7.49 (d, 9 Hz 2H), 7.24-7.20 (m, 3H), 7.11-7.01(m, 4H), 6.89 (t, 6 Hz, 2).

¹³C NMR (125 MHz, DMSO): δ=(ppm) 164.12, 164.02, 143.95, 135.74, 132.14,131.38, 130.96, 130.61, 130.37, 129.49, 128.17, 127.82, 127.60, 127.37,127.02, 126.88, 126.76, 126.57, 125.65, 125.25, 125.05, 124.23, 124.15,123.97, 123.42, 122.39

MALDI-TOF MS: C₃₀H₁₈N₂O, estimated value 422.14 g/mol, measured value422.26 g/mol.

HRMS (FAB): C₃₀H₁₈N₂O, estimated value 422.1419 g/mol, measured value422.1420 g/mol.

Example 1

As an anode, a Corning 15 Ω/cm² (1200 Å) ITO glass substrate was cutinto a size of 50 mm×50 mm×0.7 mm, ultrasonically washed for 5 minutesusing isopropyl alcohol and distilled water, irradiated with ultravioletrays for 30 minutes, and washed by exposure to ozone for 10 minutes. Theglass substrate was installed on a vacuum deposition device.

Phthalocyanine (CuPc) was vacuum deposited on top of the ITO glasssubstrate to form an HIL having a thickness of 1000 Å. On the HIL,N,N′-bis(naphthylene-1-yl)-N,N′-bis(phenyl)-benzidine (NPB) was vacuumdeposited to form an HTL having a thickness of 700 Å.

Compound 1 was vacuum deposited on the HTL to form a first emissionlayer having a thickness of 300 Å. Compound 15 was vacuum deposited onthe first emission layer to form a second emission layer having athickness of 100 Å.

Bis(2-methyl-8-quinolate-4-(phenylpenolato)aluminum (BAlq) was vacuumdeposited on the second emission layer to form an HTL having a thicknessof 200 Å, 8-hydroxyquinolinolato-lithium (LiQ) was vacuum deposited onthe HTL to form an HIL having a thickness of 10 Å, and Al was vacuumdeposited on the HIL to form a cathode having a thickness of 1000 Å,thereby completing the manufacture of an organic light-emitting device.

Example 2

An organic light-emitting device was manufactured as in Example 1,except that compound 1 and compound 15 were vacuum deposited in a weightratio of 3:1 to form an emission layer having a thickness of 400 Å(instead of a first emission layer and a second emission layer).

Comparative Example 1

An organic light-emitting device was manufactured as in Example 1,except that compound 1 was vacuum to form an emission layer having athickness of 400 Å (instead of a first emission layer and a secondemission layer).

Comparative Example 2

An organic light-emitting device was manufactured as in Example 1,except that compound 15 was vacuum deposited to form an emission layerhaving a thickness of 400 Å (instead of a first emission layer and asecond emission layer).

Comparative Example 3

An organic light-emitting device was manufactured in the same manner asin Example 1, except that compound 1 and ADN were vacuum deposited in aweight ratio of 3:1 to form an emission layer having a thickness of 400Å (instead of a first emission layer and a second emission layer).

Evaluation Example 1

External quantum efficiencies, efficiencies, power efficiencies, ELmaximum peaks, and color coordinates of the organic light-emittingdevices of Examples 1 and 2 and Comparative Examples 1 to 3 wereevaluated using a PR650 Spectroscan Source Measurement Unit(manufactured by PhotoResearch). The results are shown in Table 1.

TABLE 1 Light-emitting materials A first A second External emissionemission quantum EL layer layer efficiency λ_(max) Color materialmaterial (%) (nm) coordinates Comp. compound 1 1.1 460 0.15, 0.13Example 1 Comp. compound 15 1.2 472 0.17, 0.21 Example 2 Comp. compound1:ADN = 0.8 458 0.14, 0.15 Example 3 3:1 (w/w) Example 1 compoundcompound 2.8 468 0.15, 0.16 1 15 Example 2 compound 1:compound 3.5 4720.15, 0.19 15 = 3:1 (w/w)

According to Table 1 above, the organic light-emitting device ofExamples 1 and 2 have greater external quantum efficiencies than theorganic light-emitting devices of Comparative Examples 1 to 3.

While the present invention has been illustrated and described withreference to certain exemplary embodiments, those of ordinary skill inthe art will understand that various changes may be made to thedescribed embodiments without departing from the spirit and scope of thepresent invention as defined by the following claims.

What is claimed is:
 1. An organic light-emitting device comprising: a first electrode; a second electrode; and an organic layer between the first electrode and the second electrode, wherein the organic layer comprises an emission layer comprising at least one amine-based compound represented by Formula 1 and at least one pyrene-based compound represented by Formula 2:

wherein, in Formula 1 and 2: X₁ to X₄ are each independently a substituted or unsubstituted C₃-C₁₀ cycloalkylene group, a substituted or unsubstituted C₂-C₁₀ heterocycloalkylene group, a substituted or unsubstituted C₃-C₁₀ cycloalkenylene group, a substituted or unsubstituted C₂-C₁₀ heterocycloalkenylene group, a substituted or unsubstituted C₆-C₆₀ arylene group, or a substituted or unsubstituted C₂-C₆₀ heteroarylene group; n1 to n4 are each independently an integer of 0 to 5, and when n1 is an integer of 2 or more, the 2 or more X₁ groups are the same or different, when n2 is an integer of 2 or more, the 2 or more X₂ groups are the same or different, when n3 is an integer of 2 or more, the 2 or more X₃ groups are the same or different, and when n4 is an integer of 2 or more, the 2 or more X₄ groups are the same or different; Y₁ to Y₄ are each independently a substituted or unsubstituted C₃-C₁₀ cycloalkyl group, a substituted or unsubstituted C₂-C₁₀ heterocycloalkyl group, a substituted or unsubstituted C₃-C₁₀ cycloalkenyl group, a substituted or unsubstituted C₂-C₁₀ heterocycloalkenyl group, a substituted or unsubstituted C₆-C₃₀ aryl group, or a substituted or unsubstituted C₂-C₃₀ heteroaryl group; Z₁ and Z₂ are each independently an electron transporting group and are each independently a substituted or unsubstituted C₂-C₁₀ heterocycloalkyl group, a substituted or unsubstituted C₂-C₁₀ heterocycloalkenyl group, or a substituted or unsubstituted C₂-C₆₀ heteroaryl group; R₁ to R₄ are each independently a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a substituted or unsubstituted C₁-C₆₀ alkyl group, a substituted or unsubstituted C₂-C₆₀ alkenyl group, a substituted or unsubstituted C₂-C₆₀ alkynyl group, a substituted or unsubstituted C₁-C₆₀ alkoxy group, a substituted or unsubstituted C₃-C₁₀ cycloalkyl group, a substituted or unsubstituted C₂-C₁₀ heterocycloalkyl group, a substituted or unsubstituted C₃-C₁₀ cycloalkenyl group, a substituted or unsubstituted C₂-C₁₀ heterocycloalkenyl group, a substituted or unsubstituted C₆-C₆₀ aryl group, a substituted or unsubstituted C₆-C₆₀ aryloxy group, a substituted or unsubstituted C₆-C₆₀ arylthio group, or a substituted or unsubstituted C₂-C₆₀ heteroaryl group; a1 to a4 are each independently an integer of 0 to 4, and when a1 is an integer of 2 or more, the 2 or more R₁ groups are the same or different, when a2 is an integer of 2 or more, the 2 or more R₂ groups are the same or different, when a3 is an integer of 2 or more, the 2 or more R₃ groups are the same or different, and when a4 is an integer of 2 or more, the 2 or more R₄ groups are the same or different; and b1 and b2 are each independently an integer of 0 or
 1. 2. The organic light-emitting diode of claim 1, wherein X₁ to X₄ are each independently: i) a phenylene group, a naphthylene group, an anthracenylene group, or a fluorenylene group; or ii) a phenylene group, a naphthylene group, an anthracenylene group, or a fluorenylene group substituted with at least one of a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, or a C₁-C₁₀ alkyl group; or a C₆-C₁₆ aryl group or a C₂-C₁₆ heteroaryl group; or a C₆-C₁₆ aryl group or a C₂-C₁₆ heteroaryl group substituted with at least one of a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof a C₁-C₆₀ alkyl group, a C₂-C₆₀ alkenyl group, a C₂-C₆₀ alkynyl group, a C₁-C₆₀ alkoxy group, a C₆-C₁₆ aryl group, or a C₂-C₁₆ heteroaryl group.
 3. The organic light-emitting device of claim 3, wherein X₁ to X₄ are each independently: i) a phenylene group or a naphthylene group; or ii) a phenylene group or a naphthylene group substituted with at least one of a deuterium atom, —F, a cyano group, a nitro group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, or a tert-butyl group; an n-butyl group, an iso-butyl group, or a tert-butyl group; or iii) a phenylene group or a naphthylene group substituted with at least one of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, or a tert-butyl group substituted with at least one of a deuterium atom, —F, a cyano group, a nitro group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, or a tert-butyl group; an n-butyl group, an iso-butyl group, or a tert-butyl group; iv) a phenylene group or a naphthylene group substituted with at least one of a phenyl group, a naphthyl group, an anthracenyl group, or a fluorenyl group; or v) a phenylene group or a naphthylene group substituted with at least one of a phenyl group, a naphthyl group, an anthracenyl group, and a fluorenyl group substituted with at least one of a deuterium atom, —F, a cyano group, a nitro group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, a pyrrolyl group, an imidazolyl group, a triazolyl group, an isoindolyl group, an indolyl group, an indazolyl group, a purinyl group, a benzoimidazolyl group, an oxazolyl group, an isooxazolyl group, an oxadiazolyl group, or a benzoxazolyl group.
 4. The organic light-emitting diode of claim 1, wherein X₁ to X₄ are each independently at least one group represented by one of Formulas 4a to 4d:

wherein, in Formulas 4a to 4d: R₄₁ to R₄₄ are each independently a hydrogen atom, a deuterium atom, —F, a cyano group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, or a tert-butyl group; d1 is an integer of 0 to 4, and when d1 is a integer of 2 or more, the 2 or more R₄₁ groups are the same or different; d2 to d4 are each independently an integer of 0 to 6, and when d2 is an integer of 2 or more, the 2 or more R₄₂ groups are the same or different, when d3 is an integer of 2 or more, the 2 or more R₄₃ groups are the same or different, and when d4 is an integer of 2 or more, the 2 or more R₄₄ groups are the same or different; * is a bonding site to a pyrene ring; and *′ is a bonding site to N, Z₁ or Z₂.
 5. The organic light-emitting diode of claim 1, wherein n1 to n4 are each
 1. 6. The organic light-emitting diode of claim 1, wherein Y₁ to Y₄ are each independently: i) a phenyl group, a naphthyl group, an anthryl group, or a fluorenyl group; or ii) a phenyl group, a naphthyl group, an anthryl group or a fluorenyl group substituted with at least one of a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxylic acid group or a salt thereof, a sulfonic acid or a salt thereof, a phosphoric acid or a salt thereof, or a C₁-C₁₀ alkyl group; or a C₁-C₁₀ alkyl group substituted with at least one of a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxylic acid group or a salt thereof, a sulfonic acid or a salt thereof, or a phosphoric acid or a salt thereof; or a C₆-C₁₆ aryl group or a C₂-C₁₆ heteroaryl group; or a C₆-C₁₆ aryl group or a C₂-C₁₆ heteroaryl group substituted with at least one of a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxylic acid group or a salt thereof, a sulfonic acid or a salt thereof, a phosphoric acid or a salt thereof, a substituted or unsubstituted C₁-C₆₀ alkyl group, a substituted or unsubstituted C₂-C₆₀ alkenyl group, a substituted or unsubstituted C₂-C₆₀ alkynyl group, a substituted or unsubstituted C₁-C₆₀ alkoxy group, a C₆-C₁₆ aryl group, or a C₂-C₁₆ heteroaryl group.
 7. The organic light-emitting device of claim 1, wherein Y₁ to Y₄ are each independently: i) a phenyl group, a naphthyl group, or a fluorenyl group; or ii) a phenyl group, a naphthyl group, or a fluorenyl group substituted with at least one of a deuterium atom, —F, a cyano group, a nitro group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, or a tert-butyl group; or iii) a phenyl group, a naphthyl group, or a fluorenyl group substituted with a phenyl group, a naphthyl group, an anthracenyl group, or a fluorenyl group; or iv) a phenyl group, a naphthyl group, or a fluorenyl group substituted with at least one of a phenyl group, a naphthyl group, an anthracenyl group, or a fluorenyl group substituted with at least one of a deuterium atom, —F, a cyano group, a nitro group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, a phenyl group, a naphthyl group, an anthracenyl group, or a fluorenyl group.
 8. The organic light-emitting diode of claim 1, wherein Y₁ to Y₄ are each independently: i) a phenyl group, a naphthyl group, or a fluorenyl group; or ii) a phenyl group, a naphthyl group, or a fluorenyl group substituted with at least one of a deuterium atom, —F, a cyano group, a nitro group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, or a tert-butyl group; or iii) a phenyl group, naphthyl group, or a fluorenyl group substituted with at least one of a phenyl group, a naphthyl group, an anthracenyl group, or a fluorenyl group.
 9. The organic light-emitting diode of claim 1, wherein Y₁ to Y₄ are each independently at least one group represented by one of Formulas 5a to 5f:

wherein, in Formulas 5a to 5f: * is a bonding site to N, Z₁ or Z₂.
 10. The organic light-emitting diode of claim 1, wherein Z₁ and Z₂ are each independently: i) a pyrrolyl group, an imidazolyl group, a triazolyl group, a pyridyl group, a triazinyl group, an isoindolyl group, an indolyl group, an indazolyl group, a benzoimidazolyl group, an oxazolyl group, an isoxazolyl group, an oxadiazolyl group, or a benzoxazolyl group; or ii) a pyrrolyl group, an imidazolyl group, a triazolyl group, a pyridyl group, a triazinyl group, an isoindolyl group, an indolyl group, an indazolyl group, a benzoimidazolyl group, an oxazolyl group, an isoxazolyl group, an oxadiazolyl group, or a benzoxazolyl group substituted with at least one of a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, or a phosphoric acid group or a salt thereof, or a C₁-C₁₀ alkyl group; a C₁-C₁₀ alkyl group substituted with at least one of a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, or a phosphoric acid group or a salt thereof; a C₆-C₁₆ aryl group or a C₂-C₁₆ heteroaryl group; or a C₆-C₁₆ aryl group or a C₂-C₁₆ heteroaryl group substituted with at least one of a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C₁-C₆₀ alkyl group, C₂-C₆₀ alkenyl group, a C₂-C₆₀ alkynyl group, a C₁-C₆₀ alkoxy group, a C₆-C₁₆ aryl group, or a C₂-C₁₆ heteroaryl group.
 11. The organic light-emitting diode of claim 1, wherein Z₁ and Z₂ are each independently: i) a triazolyl group, a pyridyl group, a triazinyl group, a benzoimidazolyl group, or an oxadiazolyl group; or ii) a triazolyl group, a pyridyl group, a triazinyl group, a benzoimidazolyl group, or an oxadiazolyl group substituted with at least one of a deuterium atom, —F, a cyano group, a nitro group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, or a tert-butyl group; or iii) a triazolyl group, a pyridyl group, a triazinyl group, a benzoimidazolyl group, or an oxadiazolyl group substituted with at least one of a phenyl group, a naphthyl group, an anthracenyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, or a triazolyl group; or iv) a triazolyl group, a pyridyl group, a triazinyl group, a benzoimidazolyl group, and an oxadiazolyl group substituted with at least one of a phenyl group, a naphthyl group, an anthracenyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, and a triazolyl group substituted with at least one of a deuterium atom, —F, a cyano group, a nitro group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, a phenyl group, a naphthyl group, or an anthracenyl group.
 12. The organic light-emitting diode of claim 1, wherein Z₁ and Z₂ are each independently a group represented by one of Formulas 3a to 3i:

wherein, in Formulas 3a to 3i: R₃₁ to R₃₉ are each independently a hydrogen atom, a deuterium atom, —F, a cyano group, a methyl group, an ethyl group, a phenyl group, a biphenyl group, or a naphthyl group; c1 to c5 are each independently an integer of 0 to 4, and when c1 is an integer of 2 or more, the 2 or more R₃₁ groups are the same or different, when c2 is an integer of 2 or more, the 2 or more R₃₂ groups are the same or different, when c3 is an integer of 2 or more, the 2 or more R₃₃ groups are the same or different, when c4 is an integer of 2 or more, the 2 or more R₃₄ groups are the same or different, and when c5 is an integer of 2 or more, the 2 or more R₃₅ groups are the same or different; c6 to c8 are each independently an integer of 0 to 3, and when c6 is an integer of 2 or more, the 2 or more R₃₆ groups are the same or different, when c7 is an integer of 2 or more, the 2 or more R₃₇ groups are the same or different, and when c8 is an integer of 2 or more, the 2 or more R₃₈ groups are the same or different; and * is a bonding site to X₃ or X₄.
 13. The organic light-emitting diode of claim 1, wherein R₁ to R₄ are each independently: a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, or a C₁-C₁₀ alkyl group; or a C₁-C₁₀ alkyl group substituted with at least one of a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, or a phosphoric acid group or a salt thereof; or a C₆-C₁₆ aryl group; or a C₆-C₁₆ aryl group substituted with at least one of a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a phenyl group, a naphthyl group, or an anthryl group.
 14. The organic light-emitting diode of claim 1, wherein the amine-based compound is represented by Formula 1a and the pyrene-based compound is represented by Formula 2a:

wherein, in Formula 1a: X₁ is a phenylene group or a naphthylene group; or a phenylene group or a naphthylene group substituted with at least one of a deuterium atom, —F, a cyano group, a nitro group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, or a tert-butyl group; and Y₁ and Y₂ are each independently: i) a phenyl group, a naphthyl group, or a fluorenyl group; or ii) a phenyl group, a naphthyl group, or a fluorenyl group substituted with at least one of a deuterium atom, —F, a cyano group, a nitro group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, or a tert-butyl group; or iii) a phenyl group, a naphthyl group, or a fluorenyl group substituted with at least one of a phenyl group, a naphthyl group, an anthracenyl group, or a fluorenyl group;

wherein, in Formula 2a: X₃ is a phenylene group or a naphthylene group; or a phenylene group or a naphthylene group substituted with at least one of a deuterium atom ion, —F, a cyano group, a nitro group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, or a tert-butyl group; or Z₁ and Z₂ are each independently at least one group represented by one of Formulas 3a to 3i:

wherein, in Formulas 3a to 3i: R₃₁ to R₃₉ are each independently a hydrogen atom, a deuterium atom, —F, a cyano group, a methyl group, an ethyl group, a phenyl group, a biphenyl group, or a naphthyl group; c1 to c5 are each independently an integer of 0 to 4, and when c1 is an integer of 2 or more, the 2 or more R₃₁ groups are the same or different, when c2 is an integer of 2 or more, the 2 or more R₃₂ groups are the same or different, when c3 is an integer of 2 or more, the 2 or more R₃₃ groups are the same or different, when c4 is an integer of 2 or more, the 2 or more R₃₄ groups are the same or different, and when c5 is an integer of 2 or more, the 2 or more R₃₅ groups are the same or different; c6 to c8 are each independently an integer of 0 to 3, and when c6 is an integer of 2 or more, the 2 or more R₃₆ groups are the same or different, when c7 is an integer of 2 or more, the 2 or more R₃₇ groups are the same or different, and when c8 is an integer of 2 or more, the 2 or more R₃₈ groups are the same or different; and * is a bonding site to X₃ or X₄.
 15. The organic light-emitting diode of claim 1, wherein the amine-based compound is at least one of compounds 1 to 14, and the pyrene-based compound is at least one of compounds 15 to 21:


16. The organic light-emitting diode of claim 1, wherein the organic layer comprises: a hole transport region between the first electrode and the emission layer and having at least one of a hole injection layer, a hole transport layer, a functional layer having both hole injection ability and hole transport ability, a buffer layer, and/or an electron blocking layer; and an electron transport region between the emission layer and the second electrode and having at least one of a hole blocking layer, an electron transport layer, and/or an electron injection layer.
 17. The organic light-emitting diode of claim 1, wherein the emission layer comprises the amine-based compound and the pyrene-based compound.
 18. The organic light-emitting diode of claim 17, wherein the amine-based compound and the pyrene-based compound are co-deposited.
 19. The organic light-emitting diode of claim 17, wherein the emission layer comprises a first emission layer and a second emission layer, and the first emission layer comprises the amine-based compound, and the second emission layer comprises the pyrene-based compound.
 20. The organic light-emitting diode of claim 19, wherein the first emission layer is between the second emission layer and the first electrode. 